US9447491B2 - Coated cutting tool and method of making the same - Google Patents

Coated cutting tool and method of making the same Download PDF

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US9447491B2
US9447491B2 US14/378,371 US201314378371A US9447491B2 US 9447491 B2 US9447491 B2 US 9447491B2 US 201314378371 A US201314378371 A US 201314378371A US 9447491 B2 US9447491 B2 US 9447491B2
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cutting tool
coated cutting
coating
thickness
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US20150275348A1 (en
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Mats Ahlgren
Naureen Ghafoor
Magnus Oden
Lina Rogstrom
Mats Johansson Joesaar
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Sandvik Intellectual Property AB
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/0641—Nitrides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/04—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23C—MILLING
    • B23C5/00—Milling-cutters
    • B23C5/006—Details of the milling cutter body
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/24—Vacuum evaporation
    • C23C14/32—Vacuum evaporation by explosion; by evaporation and subsequent ionisation of the vapours, e.g. ion-plating
    • C23C14/325—Electric arc evaporation
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/04—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material
    • C23C28/042—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material including a refractory ceramic layer, e.g. refractory metal oxides, ZrO2, rare earth oxides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/04—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material
    • C23C28/044—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material coatings specially adapted for cutting tools or wear applications
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/40—Coatings including alternating layers following a pattern, a periodic or defined repetition
    • C23C28/42—Coatings including alternating layers following a pattern, a periodic or defined repetition characterized by the composition of the alternating layers
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process
    • C23C30/005—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process on hard metal substrates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23B—TURNING; BORING
    • B23B27/00—Tools for turning or boring machines; Tools of a similar kind in general; Accessories therefor
    • B23B27/14—Cutting tools of which the bits or tips or cutting inserts are of special material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23C—MILLING
    • B23C2224/00—Materials of tools or workpieces composed of a compound including a metal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23C—MILLING
    • B23C2224/00—Materials of tools or workpieces composed of a compound including a metal
    • B23C2224/36—Titanium nitride
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23C—MILLING
    • B23C2228/00—Properties of materials of tools or workpieces, materials of tools or workpieces applied in a specific manner
    • B23C2228/08—Properties of materials of tools or workpieces, materials of tools or workpieces applied in a specific manner applied by physical vapour deposition [PVD]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23C—MILLING
    • B23C2228/00—Properties of materials of tools or workpieces, materials of tools or workpieces applied in a specific manner
    • B23C2228/10—Coating
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24942—Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
    • Y10T428/2495—Thickness [relative or absolute]
    • Y10T428/24967—Absolute thicknesses specified
    • Y10T428/24975—No layer or component greater than 5 mils thick

Definitions

  • the present invention relates to coated cutting tools for chip forming machining of metals.
  • it relates to a coated cutting tool with a coating comprising a multilayer structure, which coated cutting tool has improved performance in cutting operations, in particular in cutting operations generating high temperatures.
  • the present invention relates to a method of manufacturing the coated cutting tool.
  • Cutting tools for chip forming machining of metals such as round tools, i.e. end mills, drills, etc., and inserts, made of durable materials, such as cemented carbide, cermet, cubic boron nitride or high speed steel, are commonly coated with a surface coating to prolong service life of the cutting tool. It is acknowledged that sufficient hardness of the surface coating is crucial for the wear resistance.
  • the surface coatings are mostly deposited using chemical vapour deposition (CVD) or physical vapour deposition (PVD) techniques.
  • TiN titanium nitride
  • the high hardness, the high melting point and the oxidation resistance of TiN give a dramatically improved performance and service life as compared to an uncoated cutting tool.
  • These advantageous properties have been further explored and today coatings made of different metal nitrides are used for cutting tools for different applications.
  • Al is often added to TiN, which gives an improved high temperature oxidation resistance.
  • TiAlN coatings exhibit age hardening, i.e. the hardness increases upon heat treatment. The increase in hardness is assigned to the separation of immiscible phases. Cubic TiAlN will decompose upon the heat treatment to cubic TiN and cubic AlN at about 800-900° C., which restrict dislocation motion and gives the age hardening effect. However, at higher temperatures, such as temperatures of about 1000° C., the cubic phase will be followed by a transformation into hexagonal AlN and the coating will dramatically decrease in hardness again which may be detrimental in many applications.
  • Knutsson et al., Machining performance and decomposition of TiAlN/TiN multilayer coated metal cutting inserts , Surface and Coatings Technology 205 (2011) 4005-4010 describes microstructure characterization and cutting tests of coated cutting tool inserts with PVD Ti 0.34 Al 0.66 N/TiN multilayer coatings.
  • the multilayer coatings were found to have enhanced thermal stability and improved mechanical properties as compared to homogeneous coatings of Ti 0.34 Al 0.66 N due to a more pronounced temperature induced age hardening effect and over a broader temperature range, up to about 1050° C. This improvement proved to reduce crater wear and flank wear of the cutting tool inserts as compared to the homogeneous coating. It is also disclosed that the hardness increased with decreasing multilayer period.
  • a coated cutting tool in accordance with the invention comprises a substrate, preferably made of cemented carbide, cermet, ceramic, cubic boron nitride or high speed steel, more preferably cemented carbide or cermet, and a coating on the surface of the substrate.
  • the coating comprises a multilayer structure consisting of:
  • a multilayer structure comprises at least 10, more preferably at least 30 individual layers.
  • the multilayer structure exhibits a high hardness even if subjected to temperatures of 1100° C. and thus the performance in cutting operations, in particular cutting operations generating high temperatures in the coated cutting tool, is improved.
  • the multilayer structure consists of the alternating layers A of Zr 1-x Al x N, where 0 ⁇ x ⁇ 1, and B of TiN forming the sequence A/B/A/B/A . . . .
  • heat is generated in the multilayer structure and the microstructure thereof is changed such that the coating exhibits age hardening, i.e. the hardness of the multilayer structure increases upon the heat generation.
  • This age hardening effect is maintained even after heating the multilayer structure up to at least 1100° C. due to the change in microstructure.
  • the microstructure Upon the heating of the multilayer structure the microstructure is changed such that a separation of ZrN and AlN occurs in the Zr 1-x Al x N layer and forms a layer rich in Zr and Ti at the original interface between the TiN layer and the Zr 1-x Al x N layer and an Al-rich layer in the middle of the original Zr 1-x Al x N layer.
  • there is essentially no coherency between sub-layers of the as-deposited multilayer structure at most occasionally over an interface from one sub-layer to an adjacent sub-layer and not over several interfaces.
  • the heating does not introduce columnar grains stretching over several sub-layers, at most some grains coherent across the TiN—Zr 1-x Al x N interface and through the Zr 1-x Al x N layer but at the next Zr 1-x Al x N—TiN interface the coherency is interrupted. Thanks to the changed microstructure the hardness is increased and the performance in cutting operations is improved.
  • the Zr 1-x Al x N of layer A has a low Al content where x is from 0.02 up to 0.35, preferably x is from 0.10 up to 0.35.
  • layer A comprises cubic Zr 1-x Al x N.
  • layer A consists of cubic Zr 1-x Al x N and layer B consists of cubic TiN. The lattice mismatch between cubic Zr 1-x Al x N and cubic TiN is small and thereby coherence between adjacent alternating layers is enabled and the adhesion between the adjacent alternating layers is improved.
  • the Zr 1-x Al x N of layer A has a high Al content where x is from 0.35 up to 0.90, preferably from 0.50 up to 0.90.
  • layer A comprises hexagonal Zr 1-x Al x N.
  • x being larger than 0.90 the advantageous change of the microstructure of the multilayer structure would not be recognized.
  • the Zr 1-x Al x N of layer A has a high Al content where x is from 0.60 up to 0.90, even more preferably from 0.70 up to 0.90, and the Zr 1-x Al x N is in hexagonal phase.
  • the hexagonal phase of Zr 1-x Al x N has a high hardness and high wear resistance.
  • the Zr 1-x Al x N is nanocrystalline with an average grain width of less than 10 nm, preferably less than 5 nm.
  • the individual layer thickness of layer A and layer B is larger than 5 nm and smaller than 20 nm.
  • An individual layer thickness larger than 5 nm is desired to obtain the advantageous separation of the two layers into three layers.
  • the multilayer structure has a thickness of 1-20, preferably 1-15 ⁇ m.
  • the coating is a PVD coating.
  • the coating is a CVD coating.
  • the multilayer structure consists of said alternating layers A and B with an individual layer thickness of 1-30 nm where layer A consists of Zr 1-x Al x N, where 0 ⁇ x ⁇ 1, and layer B consists of TiN and further an intermediate layer C positioned between said alternating layers A and B comprising one or more metal elements from each of the alternating layers A and B and being of different composition and structure than said alternating layers A and B.
  • layer A consists of Zr 1-x Al x N, where 0 ⁇ x ⁇ 1
  • layer B consists of TiN and further an intermediate layer C positioned between said alternating layers A and B comprising one or more metal elements from each of the alternating layers A and B and being of different composition and structure than said alternating layers A and B.
  • the intermediate layer C has a thickness being between 50 and 150% of the individual layer thickness of layer B.
  • the thickness of the intermediate layer C is at least 3 nm.
  • the intermediate layer C consists of Ti 1-y Zr y N, where y>0, preferably 0 ⁇ y ⁇ 1.
  • the composition of layer A and layer B comprises at least one additional element selected from the first, the second, the third and the fourth additional element in accordance with the following without deteriorating the advantageous hardness properties of the multilayer structure.
  • Layer A comprises first elements comprising Zr and Al and optionally first additional elements selected from one or more of Group 4a, Group 5a and Group 6a elements, Si, and Y and second elements comprising N and optionally second additional elements selected from one or more of C, O and B.
  • Layer B comprises third elements comprising Ti and optionally third additional elements selected from one or more of Group 4a, Group 5a and Group 6a elements, Si, Al and Y, and fourth elements comprising N and optionally fourth additional elements selected from one or more of C, O and B.
  • the present invention also provides a method for manufacturing a coated cutting tool comprising a substrate, preferably made of cemented carbide, cermet, ceramic, cubic boron nitride or high speed steel, and a coating on the surface of the substrate in accordance with the above embodiments comprising an intermediate layer C.
  • the method comprises the steps of:
  • the properties of the as-deposited multilayer structure of the method are in accordance with above-mentioned embodiments.
  • the coating is heat treated at at least 1000° C., preferably at least 1100° C. in non-oxidizing atmosphere to form the intermediate layer C.
  • the coating may be deposited by CVD or PVD.
  • the multilayer structure is deposited by PVD, such as sputter deposition, cathodic arc deposition, evaporation or ion plating.
  • a multilayer structure consisting of alternating layers A, B and C forming the sequence A/C/B/C/A/C/B . . . may also be accomplished by depositing these layers in sequence.
  • FIG. 1 shows the hardness of a coating in accordance with the invention as function of annealing temperature and compared to reference coatings.
  • a coated cutting tool in accordance with a first embodiment of the invention comprises a substrate and a PVD coating on the substrate.
  • the coating comprises a multilayer structure with a thickness of 1-20, preferably 1-15 ⁇ m consisting of alternating layers A and B forming the sequence A/B/A/B/A . . . with an individual layer thickness of 1-30 nm, preferably larger than 5 nm and smaller than 20 nm, where layer A consists of cubic Zr 1-x Al x N, where x is from 0.02 up to 0.35, preferably x is from 0.10 up to 0.35, and layer B consists of cubic TiN.
  • the Zr 1-x Al x N is nanocrystalline with an average grain width of less than 10 nm, preferably less than 5 nm.
  • a coated cutting tool in accordance with a second embodiment of the invention is formed from a substrate and a coating in accordance with the first embodiment and heat treated at at least 1000° C., preferably at least 1100° C. in non-oxidizing atmosphere to change the microstructure of the multilayer structure of the coating.
  • the multilayer structure consists of alternating layers A and B and an intermediate layer C positioned between layer A and layer B forming the sequence A/C/B/C/A/C/B/C/A . . . , each layer with an individual layer thickness of 1-30 nm.
  • Layer A consists of cubic Zr 1-x Al x N, where x is from 0.02 up to 0.35, preferably x is from 0.10 up to 0.35, and layer B consists of cubic TiN.
  • the Zr 1-x Al x N is nanocrystalline with an average grain width of less than 10 nm, preferably less than 5 nm.
  • Layer C comprises one or more metal elements from each of the alternating layers A and B and is of different composition and structure than said alternating layers A and B.
  • the layer C Due to separation of ZrN and AlN during the heat treatment in the Zr 1-x Al x N layer the layer C, which is rich in Zr and Ti forms at the original interface between the TiN layer and the Zr 1-x Al x N layer and an Al-rich zone is formed in the middle of the original ZrAlN layer.
  • the intermediate layer C may consist of Ti 1-y Zr y N, where y>0, preferably 0 ⁇ y ⁇ 1.
  • the preferred thickness of layer C is dependent on the heat treatment and the as-deposited individual layer thicknesses. The formation of layer C takes place at the expense of layer A.
  • the thickness of layer C is at least 3 nm, however layer C preferably has a thickness being between 50 and 150% of the individual layer thickness of layer B and layer A preferably has a thickness of at least 3 nm after heat treatment.
  • a coated cutting tool in accordance with a third embodiment of the invention comprises a substrate and a PVD coating on the substrate.
  • the coating comprises a multilayer structure with a thickness of 1-20, preferably 1-15 ⁇ m consisting of alternating layers A and B forming the sequence A/B/A/B/A . . . with an individual layer thickness of 1-30 nm, preferably larger than 5 nm and smaller than 20 nm, where layer A consist of Zr 1-x Al x N, where x is from 0.35 up to 0.90, preferably x is from 0.70 up to 0.90, and layer B consists of cubic TiN.
  • the Zr 1-x Al x N of layer A comprises hexagonal phase of Zr 1-x Al x N.
  • the Zr 1-x Al x N is nanocrystalline with an average grain width of less than 10 nm, preferably less than 5 nm.
  • a coated cutting tool in accordance with a fourth embodiment of the invention is formed from a substrate and a coating in accordance with the third embodiment and heat treated at at least 1000° C., preferably at least 1100° C. in non-oxidizing atmosphere to change the microstructure of the multilayer structure of the coating.
  • the multilayer structure consists of alternating layers A and B and an intermediate layer C positioned between layer A and layer B forming the sequence A/C/B/C/A/C/B/C/A . . . , each layer with an individual layer thickness of 1-30 nm.
  • Layer A consists of hexagonal Zr 1-x Al x N, where x is from 0.35 up to 0.90, preferably x is from 0.70 up to 0.90, and layer B consists of cubic TiN.
  • the Zr 1-x Al x N is nanocrystalline with an average grain width of less than 10 nm, preferably less than 5 nm.
  • Layer C comprises one or more metal elements from each of the alternating layers A and B and is of different composition and structure than said alternating layers A and B.
  • the layer C Due to separation of ZrN and AlN during the heat treatment in the Zr 1-x Al x N layer the layer C, which is rich in Zr and Ti forms at the original interface between the TiN layer and the Zr 1-x Al x N layer and an Al-rich zone is formed in the middle of the original ZrAlN layer.
  • the intermediate layer C may consist of Ti 1-x Zr x N, where y>0, preferably 0 ⁇ y ⁇ 1.
  • the preferred thickness of layer C is dependent on the heat treatment and the as-deposited individual layer thicknesses. The formation of layer C takes place at the expense of layer A.
  • the thickness of layer C is at least 3 nm, however layer C preferably has a thickness being between 50 and 150% of the individual layer thickness of layer B and layer A preferably has a thickness of at least 3 nm after heat treatment.
  • a coating consisting of alternating layers of Zr 0.65 Al 0.35 N and TiN was deposited by cathodic arc deposition on a polished CNMG 120408-MM substrate made of WC-Co 10 wt-% Co cemented carbide using an Oerlikon Balzers RCS system to form coated cutting tools.
  • a Zr 0.65 Al 0.35 target and a Ti target serving as cathodes were placed at opposite sides of the vacuum chamber of the system. Substrates were loaded in the vacuum chamber and deposition was performed at 400° C.
  • the coating thickness was 2.6 ⁇ m on the flank side.
  • the coating thickness was about 2-3 ⁇ m.
  • the deposition time was the same as in Example 2 and hence the coating thickness was about the same.
  • a coating consisting of a single-layer of Zr 0.65 Al 0.35 N was deposited by cathodic arc deposition as described in Example 1 but using only a Zr 0.65 Al 0.35 target and without rotation.
  • the deposition time was the same as in Example 2 and hence the and hence coating thickness was about the same.
  • the structure of as-deposited and annealed films was studied by x-ray diffraction using a PANalytical Empyrean diffractometer.
  • the mechanical properties were characterized by nanoindentation using a UMIS 2000 system equipped with a Berkovich indenter. Polished, tapered (about 5°) cross sections of the films were prepared and a minimum of 20 indents were made in each sample using a load of 40 mN. The data was analyzed by the method of Oliver and Pharr (W. C. Oliver, G. M. Pharr, J. Mater. Res. 7 (1992) 1564) and the mean value and standard deviation from the 20 measurements was determined.
  • FIG. 1 shows the hardness as a function of annealing temperature of the multilayered coatings of Examples 2, 3 and 4 and the single-layer coating of Example 5.
  • the hardness of the as-deposited single-layer Zr 0.65 Al 0.35 N coating of Example 5 is 23 GPa and is stable up to annealing temperatures of 1000° C.
  • the highest hardness, 30 GPa is found for the coating with the shortest period.
  • Annealing of both the Zr 0.65 Al 0.35 N/ZrN coatings at 800° C. causes the hardness to increase, but after annealing at higher temperatures the hardness is lower again.
  • X-ray diffractograms of the as-deposited multilayered Zr 0.65 Al 0.35 N/ZrN coatings showed broad and asymmetric peaks from cubic ZrN.
  • X-ray diffractograms of the annealed multilayered Zr 0.65 Al 0.35 N/ZrN coatings showed narrower peaks that were shifted to higher angles. Any peaks from cubic ZrAlN in the multilayered Zr 0.65 Al 0.35 N/ZrN coatings overlap with the peaks from the cubic ZrN.
  • TEM studies showed that a separation of ZrN and AlN had occurred in the Zr 1-x Al x N layer giving an Al rich layer in the middle of the Zr 1-x Al x N layer and Zr-rich layers at the original Zr 1-x Al x N—ZrN interfaces.
  • the multilayered Zr 0.65 Al 0.35 N/ZrN coating is at least partly coherent across the Al- and Zr-rich layers and large cubic grains have developed that continues over several sub-layers.
  • the TEM studies further showed that no hexagonal phases were present in the annealed multilayered Zr 0.65 Al 0.35 N/ZrN coatings and further that a separation of ZrN and AlN had occurred.
  • the as-deposited multilayered Zr 0.65 Al 0.35 N/TiN coating showed diffraction peaks from both cubic TiN and cubic ZrAlN.
  • the peaks from the c-ZrAlN phase were broad.
  • Annealing at 800° C. the diffraction peaks from both phases were narrowed and the peaks from cubic TiN were shifted to higher angles.
  • Annealing at 1000° C. caused the diffraction peaks of the cubic ZrAlN phase to move to higher angles, while no change is observed for the cubic TiN peaks.
  • a coating consisting of alternating layers of Zr 0.65 Al 0.35 N and TiN was deposited on a CNMG 120408-MM substrate made of WC-Co 10 wt-% Co cemented carbide by cathodic arc deposition as described in Example 1 but with a three-fold substrate rotation.
  • the coating thickness was 2.2 ⁇ m on the flank side and 1.7 ⁇ m on the rake side, as determined by cross-sectional light optical microscopy.
  • a coating consisting of alternating layers of Zr 0.65 Al 0.35 N and TiN was deposited on a CNMG 120408-MM substrate made of WC-Co 10 wt-% Co cemented carbide by cathodic arc deposition as described in Example 2 but with a three-fold substrate rotation.
  • the coating thickness was 2.6 ⁇ m on the flank side and 1.9 ⁇ m on the rake side.
  • a coating consisting of alternating layers of Zr 0.50 Al 0.50 N and TiN was deposited as described in Example 7 but with a Zr 0.50 Al 0.50 target instead of a Zr 0.65 Al 0.35 target.
  • the coating thickness was 1.5 ⁇ m on the flank side and 1.0 ⁇ m on the rake side.
  • a coating consisting of alternating layers of Zr 0.17 Al 0.83 N and TiN was deposited as described in Example 7 but with a Zr 0.17 Al 0.83 target instead of a Zr 0.65 Al 0.35 target.
  • the coating thickness was 1.7 ⁇ m on the flank side and 0.9 ⁇ m on the rake side.
  • a single-layer coating consisting of Ti 33 Al 77 N was deposited as described in Example 6 using only a Ti 33 Al 77 target at a pressure of 10 ⁇ bar and ⁇ 100 V substrate bias.
  • the coating thickness was 4.79 ⁇ m on the flank side and 3.2 ⁇ m on the rake side.
  • the coated cutting tools of Examples 6-10 were evaluated with respect to crater wear in a continual longitudinal turning operation in ball bearing steel (Ovako 825B) with depth of cut 2 mm, cutting speed 160 m/min, feed speed 0.3 mm/rev and using coolant.
  • the stop criteria was crater area of 0.8 mm 2 and cutting times required to reach this criteria are indicated in Table 1.

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Cited By (1)

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US20200238412A1 (en) * 2019-01-25 2020-07-30 Snap-On Incorporated Method of manufacturing socket punches

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JP6535922B2 (ja) * 2015-11-25 2019-07-03 住友電工ハードメタル株式会社 表面被覆切削工具の製造方法
CN105773462B (zh) * 2016-01-07 2019-03-29 北京师范大学 一种基于离子束技术提高抛光光学玻璃的金刚石砂轮棒寿命的方法及设备
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RU2694857C1 (ru) * 2018-08-06 2019-07-18 федеральное государственное бюджетное образовательное учреждение высшего образования "Уфимский государственный авиационный технический университет" Способ нанесения износостойкого покрытия ионно-плазменным методом
WO2020070967A1 (ja) * 2018-10-03 2020-04-09 住友電工ハードメタル株式会社 表面被覆切削工具及びその製造方法
WO2020254424A1 (en) * 2019-06-19 2020-12-24 Ab Sandvik Coromant A coated cutting tool
CN116372206B (zh) * 2023-03-09 2024-03-19 株洲肯特硬质合金股份有限公司 一种刀具用纳米涂层及涂层刀具

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0603468A1 (de) * 1992-12-24 1994-06-29 Dürkopp Adler Aktiengesellschaft Hängeförderanlage mit einer Ausschiebevorrichtung mit Überlastfunktion
US5503912A (en) * 1992-10-12 1996-04-02 Sumitomo Electric Industries, Ltd. Ultra-thin film laminate
US6395379B1 (en) * 1996-09-03 2002-05-28 Balzers Aktiengesellschaft Workpiece with wear-protective coating
US6506999B2 (en) * 1997-12-18 2003-01-14 Hartec Gesellschaft Fur Hartstoffe Und Dunnschichttechnik Mbh & Co Kg Laminate system, a process for the production thereof and use thereof
US20070111032A1 (en) * 2005-11-11 2007-05-17 Mitsubishi Heavy Industries, Ltd. Surface-coated article, production method therefor, machine tool, and machine tool apparatus
WO2007136777A2 (en) 2006-05-17 2007-11-29 G & H Technologies Llc Wear resistant coating
EP1935999A2 (en) * 2006-12-15 2008-06-25 Sandvik Intellectual Property AB Coated cemented carbide endmill
EP2098611A2 (en) 2008-03-07 2009-09-09 Seco Tools Ab Layered coated cutting tool
WO2009151386A1 (en) * 2008-06-13 2009-12-17 Seco Tools Ab Coated cutting tool for metal cutting applications generating high temperatures
WO2010114448A1 (en) 2009-04-03 2010-10-07 Sandvik Intellectual Property Ab Coated cutting tool for metal cutting applications generating high temperatures
US20120090247A1 (en) * 2009-06-22 2012-04-19 Tungaloy Corporation Coated Cubic Boron Nitride Sintered Body Tool

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3460287B2 (ja) * 1994-01-21 2003-10-27 住友電気工業株式会社 耐摩耗性に優れた表面被覆部材
JP4185172B2 (ja) * 1997-06-19 2008-11-26 住友電工ハードメタル株式会社 被覆硬質工具
RU2191220C2 (ru) * 2000-08-14 2002-10-20 Уральский электрохимический комбинат Износостойкое покрытие
RU2433209C1 (ru) * 2010-06-15 2011-11-10 Государственное образовательное учреждение высшего профессионального образования "Пермский государственный технический университет" Способ получения износостойкого и термодинамически устойчивого многослойного покрытия на основе тугоплавких металлов и их соединений

Patent Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5503912A (en) * 1992-10-12 1996-04-02 Sumitomo Electric Industries, Ltd. Ultra-thin film laminate
EP0603468A1 (de) * 1992-12-24 1994-06-29 Dürkopp Adler Aktiengesellschaft Hängeförderanlage mit einer Ausschiebevorrichtung mit Überlastfunktion
US6395379B1 (en) * 1996-09-03 2002-05-28 Balzers Aktiengesellschaft Workpiece with wear-protective coating
US6506999B2 (en) * 1997-12-18 2003-01-14 Hartec Gesellschaft Fur Hartstoffe Und Dunnschichttechnik Mbh & Co Kg Laminate system, a process for the production thereof and use thereof
US20070111032A1 (en) * 2005-11-11 2007-05-17 Mitsubishi Heavy Industries, Ltd. Surface-coated article, production method therefor, machine tool, and machine tool apparatus
US20070284255A1 (en) * 2006-05-17 2007-12-13 Vladimir Gorokhovsky Wear resistant vapor deposited coating, method of coating deposition and applications therefor
WO2007136777A2 (en) 2006-05-17 2007-11-29 G & H Technologies Llc Wear resistant coating
EP1935999A2 (en) * 2006-12-15 2008-06-25 Sandvik Intellectual Property AB Coated cemented carbide endmill
EP2098611A2 (en) 2008-03-07 2009-09-09 Seco Tools Ab Layered coated cutting tool
US20090226273A1 (en) * 2008-03-07 2009-09-10 Seco Tools Ab Layered Coated Cutting Tool
WO2009151386A1 (en) * 2008-06-13 2009-12-17 Seco Tools Ab Coated cutting tool for metal cutting applications generating high temperatures
WO2010114448A1 (en) 2009-04-03 2010-10-07 Sandvik Intellectual Property Ab Coated cutting tool for metal cutting applications generating high temperatures
US20120114442A1 (en) * 2009-04-03 2012-05-10 Sandvik Intellectual Property Ab Coated cutting tool for metal cutting applications generating high temperatures
US20120090247A1 (en) * 2009-06-22 2012-04-19 Tungaloy Corporation Coated Cubic Boron Nitride Sintered Body Tool

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
Dejun "Synthesis of ZrAIN coatings with thermal stability at high temperature" Science in China Series E:Tech Sci 2006 vol. 49 No. 5 p. 576-581. *
Franz R et al: "Oxidation behaviour and tribological proerties of arc-evaporated ZrAIN hard coatings",Surface and Coatings Technology, vol. 206, No. 8-9, Jan. 15, 2012 pp. 2337-2345.
Hasegawa et al: Effects of Al contents on microstructures of Cr1-xAlxN and Zr1-xAlxN films synthesized by cathodic arc method.
Lamni et al "Microstructure and nanohardness properties of Zr-Al-N and Zr-Cr-N thin films" J. Vac. Sci. Technol. A 23(4) Jul./Aug. 2005. *
Rogstromr et al: "Age hardening in arc-evaporated ZrAIN thin films",Scripa Materialia, vol. 62, (2010) pp. 739-741.

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20200238412A1 (en) * 2019-01-25 2020-07-30 Snap-On Incorporated Method of manufacturing socket punches
US10987745B2 (en) * 2019-01-25 2021-04-27 Snap-On Incorporated Method of manufacturing socket punches

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